Homoenolate Anions

Bicyclooctanone Rearrangement, [3.2.1] → [3.3.0], via β-Enolization. Evidence for γ-Enolization in Bicyclo[3.3.0]octan-2-one

“…Nevertheless the process has synthetic utility (2) and warrants further investigation to define its scope more precisely in terms of suitable molecular geometries and the stereochemistry of ketonization. At present these features are established only for the bicyclo[2.2.1]heptan-2-one skeleton (1,3) and adamantanone (4) 4While hornoenolization neatly describes the process at fi carbons, more remote proton abstraction can occur. We suggest, therefore, a more general term to specify the reaction site.…”

Synthesis of insect pheromones: Improved method for the preparation of queen substance and royal jelly of honeybeesApis mellifera

“…Since Nickon and Lambert introduced the concept of homoenolate anions in 1962 (Nickon & Lambert 1962), the homoenolates and their synthons have been used in many organic synthesis applications (for recent reviews see Nair et al 2008;Hoppe 2009). As a part of a program aimed at developing new homoenolate synthons, we have reported on the synthetic utility of lithium anions derived from allylphosphoramides as aldehyde (Coutrot et al 1993(Coutrot et al , 1994(Coutrot et al , 1999 and ketone (Grison et al , 2004 homoenolate equivalents.…”

An examination of β-enolization in benzobicyclo[2.2.2], [3.2.1], and [3.2.2] ketones

“…-2-(11,2',3',4'-terrahydro-1 '-naphthy1) 3,3-Dimethyl-6,7-benzobicyclo[3.3.O]octet1-2-0t~e (20) The new ketone was separated from 8 by preparative tlc on Silica Gel 60 F-254 plates (0.5 rnm) with petroleum ether -ether (90: 10) as eluent and was assigned structure 20 from the follow- The ketone obtained from 9 was purified by tlc, as described above for 20, and recrystallized from aqueous EtOH, mp 112-115°C. It was assigned structure 25 on the basis of the following data: ir (CHC1,): 1698 cm-'; 'Hmr (CDCI,) 6: 0.49 (s, 3H, endo-3-Me), 1.09 (s, 3H, exo-3-Me), 1.95 (dt, lH, J = 13.6, 2.7 Hz, endo-H-4), 2.05 (dd, 1 acid (72) The single acid isolated from the runs with 9 was purified by recrystallization from EtOH to yield white needles, mp 87-88"C, and identified as 27 on the basis of the following data: ir (CHCI,): 2400-3400, 1698 cm-'; 'Hmr (CDCI,) 6: 1.33 (s, 3H, 2-Me), 1 …”